Blue sulfur dye and process of making same.



llmrno STATES Patented November 29, 1904.

PATENT ALBRECHT SCHMIDT AND FRITZ BETHMA'NN, OF HOOHST-ON-THE-MAIN,

GERMANY, ASSIGNORS TO FARBWERKE, VORM. MEISTER. LUOIUS &,

BRIINING, OF HOCHST ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY.

BLUE SULFUR DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 776,264, dated November 29, 1904.

Application filed March 3, 1903.

To all whom, it may concern.-

Be it known that we, ALBRECHT SCHMIDT, Ph. D., and FRITZ BETHMANN, Ph. D., citi- Zens of the Empire of Germany, residing at Hochst-on-the-Main, Germany, have invented certain new and useful Improvements in the Manufacture of Blue Sulfurized Dyestuffs, of which the following is a specification.

WV e have found that by heating dialkylpara-amido para -oxy meta chlordiphenylamins with sulfur and alkali sulfids in the proportion of more than one part, by Weight, of sulfur to four parts of sulfid of an alkali metal, (French Patent No. 803,524,) preferably in presence of a solvent at a temperature of below 100 centigrade, they are transformed into clear blue sulfuriZed dyestuffs of greater intensity and more valuable properties than the dyestulfs obtained by said French patent. Our dyestuffs have proved to be free from chlor'in. The parent materials may be obtained, for instance, by oxidizing diethylpara-phenylenediamin with ortho-chlorphenol and reducing the chlorinated indophenol thus obtained.

Example I: Sixty parts, by Weight, of dimethyl para-amido para -oxymeta -chlordiphenylamin (about eighty-two parts of moisture) are heated in a reflux apparatus with two hundred parts of sodium sulfid, sixty parts of glycerin, eighty-four parts of sulfur, and twenty parts of water, preferably in the presence of some alcohol. The limit of inside temperature is about 94 Soon there is a rapid elimination of hydrogen sulfid and separation of the product. After about twenty hours the mixture is diluted with water, when the product separates completely. The latter is filtered and washed. The dyestuff needs no further purification. It is diluted only with sulfur, but dyes, even in the raw unpurified state, a blue of very clear indigo-like shade. The dyestuif freed from sulfur by redissolving in the usual manner is a violetblack powder insoluble in Water, which on I Serial No. 146,001. (Specimens) rubbing assumes a metallic luster. Concentrated sulfuric acid dissolves it to a blue solution, also alcohol, but only in slight degree. 1Sullids of alkali metals dissolve it easily when 1ot.

For dimethyl-para-amido-para -oxymeta chlordiphenylamin,though less advantageous, may be substituted the corresponding indophenol. The corresponding diethylamido compound behaves in a similar manner.

Example II: Ninety-eight parts of phenol are dissolved in one hundred and eighteen parts of concentrated caustic-soda lye and two thousand parts of water. Into this solution is run the calculated quantity of chlorid of lime, (one-half molecular proportion of chlorid of lime for one molecular proportion of phenol.) After the chlorination the solution containing chlorphenol is separated by filtration, with or without previous precipitation of the dissolved lime with sodium carbonate, &c. The alkaline solution is then mixed with the dimethyl-para-phenylenediamin solution obtained from one hundred and fifty parts of nitroso-dimethylanilin after having neutral ized the greater part of the caustic alkali formed, and this in such a manner that the chlorphenol remains still dissolved in the alkaline solution. Then is run in while stirring and cooling at about 10 centigrade a solution of sodium hypoehlorite until the oxidation is complete. The chlorindophenol is allowed to deposit, filtered, and reduced by heating with a solution of sodium sullid to dimethyl-para-amido para oxy -meta -chlordi phenylamin. The indophenol thus obtained may also directly be introduced into the sodium-sulfid mass.

Example III: Dyestuffs apparently identiby isolating the chlorinated beautifully-crystallized indophenolthiosulfonic salt in the usual manner.

Having now described our invention, What We claim is 1. The herein-described process for the manufacture of blue sulfurized dyestuffs, which consists in heating dialkyl-para-amido-para oxy-meta -chlordiphenylamin with sulfur and sulfids of alkali metals in the proportion of more than one part of sulfur to four parts of crystallized sodium sulfid.

2. The herein-described process for the manufacture of blue sulfurized dyestuffs, which consists in heating the corresponding indophenols or thiosulfonic acids of dialkyl-paraamido para oXy meta chlordiphenylamin with sulfur and sulfids of alkali metals in the proportion of more than one part of sulfur to ALBRECHT SCHMIDT. FRITZ BETHMANN.

W'itnesses ALFRED BmsBols, BERNHARD LEYDEOKER. 

